Germicidal alkylhalodiphenyl oxide sulfonate compositions



United States Patent Ofice This application is a division of ourcopending application, Serial No. 842,583, filed September 28, 1959, nowPatent No. 3,110,683, which in turn is a continuation-in-part ofapplications, Serial No. 744,008, filed June 23, 1958, now Patent No.2,992,999, Serial Nos. 735,669 and 735,681, filed May 16, 1958, nowabandoned and Serial No. 816,061, filed May 27, 1959, now abandoned.

This invention relates to alkylated halogenated sulfonated diphenylioxides; i.e., to compounds having diphenyl oxide'as a nucleus. to whichare attached a longchain alkyl 'radical,'one or two halogens, and oneor' two sulfonic acid radicals. These compounds are those having thegeneric formula R[ I I X (s0.H)..

LU OJ wherein R represents an alkyl radical containing 12 to 22 carbon.atoms; X represents a halogen of atomic num- [ber 17 to 53, i.e.,chlorine, bromine or iodine; and, m and n are integers from 1 to 2; and,salts thereof.

The soluble compounds of the invention are highly surface-active. Thus,the lithium, sodium, potassium, ammonium and most amine salts arereadily soluble in water and are useful as detergents, wetting agents,emulsifying and dispersing agents and the like. Many are soluble inpetroleum oils and distillates and in various organic fluids. Thepolyvalent metal salts are substantially insoluble in water but aregenerally soluble in various organic solvents, including petroleum oils.

was cooled, washed with water and distilled at 0.8 mm.

pressure.

Solutions in the latter are particularly useful as corrosion inhibitorsfor ferrous metals as well as being effective oilsoluble surfactants.

The compounds of the invention may be prepared in a variety of ways.Thus, diphenyl oxide may be alkylated, halogenated and sulfonated in anydesired sequence to produce the sulfonic acids. The latter may then beconverted to any desired salt thereof by reaction with the appropriatebase or salt. Alternatively, either or both of the benzene rings of thediphenyl oxide nucleus may be appropriately alkylated and/or halogenatedbefore being condensed to form the diphenyl oxide nucleus. Some of thesemethods are illustrated by the following examples.

EXAMPLE 1.-DODECYLDICHLORODIPHENYL OXIDE SULFONATE Step (1) Preparationof dichlorodiphenyl oxide.-- Chlorine was sparged into diphenyl oxidecontaining 1% by weight of ferric chloride, the temperature being main-Step (3) Sulfo'nation of alkyldichlorodiphenyl oxide.- One tenth mole ofdodecy ldichlorodiphenyl oxide obtained from Step (2) was dissolved in200 ml. of methylene chloride. The solution was maintained at 9-17 C.while a solution of 10.4 grams of sulfur trioxide in ml. of methylenechloride was slowly added with stirring. Fifteen minutes after theaddition was complete,

350 ml. of water was added with stirring and the mixturewas thenneutralized with 50% aqueous sodium hydroxide. Theaqueous and organiclayers were separated and the latter was dried and the solventevaporated, thus leaving a solid which was then ground to a tan powder.It was readily soluble in water and ethanol.

Various homologs and analogs of the above product were prepared bysubstantially the same procedure. Thus, when the tetrapropyleue used inStep (2) above was replaced with an equivalent amount of higher olefinscontaining up to 22 carbon atoms, the correspondinga'l-kyldichlorodiphenyl oxide sulfonates were obtained. They hadproperties generally similar to those of the dodecyl homolog but weremore readily soluble in organic solvents, especially in hydrophobicsolvents. When primary-alkyl-substituted products were desired thediphenyl oxide or halogenated diphenyl oxide was alkylated by using thealkanoyl chloride (e.g., lauroyl chloride) and aluminum chloride andthen hydrogenating the thus formed acyl diphenyl oxide to thecorresponding lalkyl derivative.

In another manner of preparing the compounds of the present invention, ahalobenzenecompound which may contain one tothree halogen substitutents.is mixed. or otherwise blended with a phenol (by the term phenol, it isto be understood that this term is inclusive of phenol and halophenol)in the presence of a catalytic amount of copper and/or mercury and astrong alkali and preferably in the presence of an inert organicsolvent. The

reaction proceeds smoothly at about the reflux temperature of themixture with the production of the desired product and water ofreaction. The water of reaction is azeotropically removed from thereaction zone as formed. Upon near completion of the reaction, asevidenoed .by the substantial cessation of the formation of water ofreaction, the temperature of the reaction mix-1 ture is raised to aboutl50-160 C. for a period of time to complete the reaction. The mixture isthereafter cooled to about C., filtered while hot, water added andpermitted to stand, whereupon aqueous and organic layers form. Thedesired product is obtained from the organic layer and is employed inthe preparation of the alkyl'halodiphenyl oxide by alkylation with anolefin in the presence of anhydrous aluminum chloride. The reactionmixture upon completion of the latter reaction mixture separates into 2layers, i.e., organic and aqueous.

The desired product is again removed from the organic layer and employedin the sulfonation step to prepare the alkylhalodiphenyl oxidesulfonate. The sulfonation may be carried out employing sulfur trioxideor oleum and is preferably carried out by employing sulfur trioxide inan inert solvent, such as methylene chloride or perchloroethylene. I

EXAMPLE 2.SODIUM 4-CHLORO-4-DODECYL- DIPHENYL OXIDE SULFONATE Step (IPreparation of 4-chlor0diphenyl 0xide.-1700 grams (8.9 moles) ofl-bromo-4-chlorobenzene was mixed with 740 grams (7.85 moles) of phenoland one-half gram of mercury, and dispersed in ml. of toluene containing10 grams of copper bronze powder. The resulting mixture was heated tothe reflux temperature Patented Apr. 12, 1966 3 (130 C.) and 380 gramsof potassium hydroxide added slowly. The water of reaction wasazeotropically distilled and removed from the reaction zone. When mostof the water of reaction had been removed the major portion of thebenzene remaining was also removed and the temperature of the reactionmixture was raised to 150 C. for 2 hours and then to 160 C. for 1 hour.Thereafter, the mixture was cooled to about 90 C. and water added todissolve the salts which had formed. Filteraid was added, the mixturewas filtered hot and the filtrate permitted to separate into a waterlayer and an organic layer. The water layer was separated and washedwith ethylene dichloride and the extract added to the organic layer. Theorganic layer was fractionally distilled under reduced pressure toobtain a 4-chlorodiphenyl oxide product boiling at l33-139 C. at mm.pressure.

Step (2) Preparation of 4-chloro-4'-dodecyldiphenyl oxide-76.6 grams(0.375 mole) of 4-chlorodiphenyl oxide prepared in the manner of Step(1) and 3.6 grams of anhydrous aluminum chloride were mixed together andheated to 60 C. While maintaining this temperature, 42.0 grams (0.25mole) of tetrapropylene were added slowly, portionwise, over a one-hourperiod. Upon completion of the addition, the reaction mixture was heatedfor anadditional hour with stirring. Thereafter, the reaction mixturewas diluted with an equal volume of water and, upon standing, thereaction mixture separated into two layers. The aqueous layer wasseparated and discarded; the organic layer washed with a 1 aqueoussolution of NaHCO then with water-methylene chloride solution, andsubsequently dried over CaCl The resulting product was tractionallydistilled under reduced pressure to obtain a 4-chloro-4'-dodecy1diphenyloxide product having a boiling range of 190-235 C. at 5 mm. pressure.

Step (3) Preparation of 4-chloro-4'-dodecyldiphenyl oxide sodiumsulfonate.-5.2 grams (0.065 mole) of S0 dissolved in 50 ml. of methylenechloride were added with stirring over a -minute period to 18.65 grams(0.05 mole) of, the product of Step (2) dissolved in 100 ml. ofmethylene chloride. The temperature was maintained at 23 C. throughoutthe addition by external cooling of the reaction vessel in an ice-waterbath. The stirring was continued for an additional 15 minutes, afterwhich 150 ml. of water was added and the reaction mixture neutralized topH 7.0 by adding sodium hydroxide. The entire mixture was oven-dried at100 C. and thereafter extracted with 1 liter of absolute ethyl alcoholand the alcohol evaporated from the extract to obtain a sodium4-chloro-4'-dodecyldiphenyl oxide sulfonate product as an otf-whitesolid having a softening range of 120- 135 C. EXAMPLE 3.-PREPARATION OFCOMMERCIAL SODIUM 4 CHLORO 4' DODECYLDIPHENYL OXIDE SULFONATE Step (1)Preparation of 4-chl0r0diphenyl 0xid e.680 grams (4 moles) of diphenyloxide and 7 grams of fine steel wool were placed in a reaction vesselwhich was provided with an external cooling means. The entire reactionvessel and cooling bath were covered to exclude light. Chlorine gas wasbubbled through the reaction mixture until the. specific gravity reached1.18. During the addition of the chlorine gas, the reaction mixture wasmaintained at a temperature of about 40 C. Subsequently, air was blownthrough the reaction mixture to remove the excess chlorine and HCl. Thecrude product was washed with 10% sodium bicarbonate solution and thenwith water. It was then diluted with an equal volume of methylenechloride, dried over calcium chloride, filtered and distilled underreduced pressure. As a result of these operations there was obtained 265grams of product boiling at 136 C. 3" C. at 5 mm. pressure. The productconsisted of a mixture of 12% of 2-chlorodiphenyl oxide and 88% of4-chlorodiphenyl oxide.

Step (2) Preparation of 4-chloro-4'-dodecyldiphenyl oxide-Employing thereaction product of Step (1) above in the manner of Step (2) of Example2 to alkylate the product there is obtained a4-chloro-4'-dodecyldiphenyl oxide product (containing 12% Z-chloroderivatives) boiling at 184-188 C. at 1.1-1.6 mm. pressures.

Step (3) Preparation of sodium 4-chIoro-4'-dodecyldiphenyl oxidesulf0nate.Employing the procedure of Step (3) of Example 2, the productof Step (2) above was sulfonated to obtain a sodium4-chloro-4'-dodecyldiphenyl oxide sulfonate product (containing 12% 2-chloro derivative) as a light tan crystal having a softening point of-l35 C.

In the manner of the Example 3, employing appropriate startingmaterials, sodium pentadecylchlorodiphenyl oxide sulfonate was obtainedas a paste having a softening point of 56-60 C.

EXAMPLE 4.-SULFONATION OF THE ALKYL- ATED CHLORODIPHENYL OXIDE WITH 20PERCENT OLEUM One-tenth mole of 4-chloro-4-dodecyldiphenyl oxide (88%4-chloro and 12% 2-chloro isomer) and 100 ml. of methylene chloride wereplaced in a cooled reaction zone with a stirrer; 50 grams of 20% oleumwas slowly added portionwise over a period of 15 minutes with stirringand at a temperature of 18-25 C. Stirring was continued for anadditional 15 minutes. Thereafter the reaction mixture waspermitted tosettle and formed an organic layer above the unused acid which later wasremoved. The organic layer was dropped into milliliters of water andneutralized with 30 percent aqueous caustic to a pH 7.0-7.5. The mixturewas permitted to settle and the organic lower layer recovered and dried.The sodium 4-chloro-4'-dodecyldiphenyl oxide sulfonate product(containing 12% of the 2-chloro isomer) was an oif-white color and had asoftening point of 104-107 C.

In the manner of Example 3, employing the appropriate startingcompounds, other haloalkyldiphenyl oxide sulfonate salts may be preparedas for example, the sulfonates of docosylchlorodiphenyl oxide,eicosylchlorodiphenyl oxide, dodecylbromodiphenyl oxide,tetradecylbromodiphenyl oxide, dodecyliododiphenyl oxide, and the like.

EXAMPLE 5.SODIUM 4-CHLORO-4'-DODECYL- DIPHENYL OXIDE DISULFONATE Step (IPreparation of 4-chlorodiphenyl oxide-2.375 pounds of diphenyl oxide and22.7 pounds of anhydrous ferric chloride were placed in a reactionvessel which was provided with an external cooling means. The entirereaction vessel and cooling bath were covered to exclude light. Chlorinegas was bubbled through the reaction mixture until the specific gravityreached 1.203. During the addition of chlorine gas the reaction mixturewas continuously stirred and the reaction temperature was maintained atabout 40 C. Subsequently air was blown through the reaction mixture toremove the excess chlorine and HCl. The crude product was washed with 13pounds of sodium carbonate as an aqueous solution and volthen withwater. It was then diluted with an e tune of methylene chloride, driedover calcium chloride, filtered, and the solvent distilled to obtain2768 pounds of crude product. 82 pounds of this crude product wasdistilled under reduced pressure to obtain 45.3 pounds of productboiling at 124-134 C. at 3.3 mm. pressure. The product consisted of amixture of 17% of 2-chlorodiphenyl oxide and 83% of 4-ohlorodiphenyloxide.

Step (2) Preparation of 4-chloro-4'-dodecyldiphenyl oxide.511 grams ofchlorodiphenyl oxide prepared in the manner of Step (1) and 22.3 gramsof anhydrous aluminum chloride were mixed together and dry hydrogenchloride bubbled into the mixture for '5 minutes. Thereafter thereaction vessel and contents were heated to 60 C. While maintaining thistemperature, 280 grams of I mixture was stirred for one-half hour.

tetrapropylene were added slowly, portionwise, over a one-hour period.Upon completion of the addition, the reaction mixture was heated for anadditional 2 hours with stirring. Thereafter, the reaction mixture wasagi- -tated with an equal volume of 30% sodium hydroxide solution. Uponstanding, the reaction mixture separated into two layers. The aqueouslayer was separated and discarded while the organic layer was washedwith a aqueous solution of NaI-ICO and then with water-methylenechloride solution and subsequently dried over CaCl After distillation ofthe solvent the resulting crude product (778 grams) was fraotionallydistilled under reduced pressure to obtain a 4-chloro-4-dodecyldiphenyloxide product (17% ortho-chloro and 83% para-chloro) having a boilingrange of 170-180 C. at 1.5 mm. pressure.

In the manner of the Step 2) employing the appropriate startingmaterials, the following compounds were obtained having the followingproperties.

Alkylhalodiphenyl oxides Boiling temperatures Pentadecylchlorodiphenyloxide 182210 C. at .4.9

Dodecylbromodu'phenyl oxide ZOO-240 C. at 5 mm.

Step (3) Disodium dodecylchlorodiphenyl oxide disulfonate.37.3 grams ofdodecylchlorodiphenyl oxide was dissolved in 500 grams of methylenechloride and then cooled in an ice bath to below 27 C. There was added asolution of 20 grams of sulfur trioxide in 266 grams of methylenechloride with stirring over a period of minutes. After the addition wascomplete, the reaction Thereafter, onehalf liter of water was added andthe mixture was neutralized with 50% sodium hydroxide. The methylenechloride layer which formed was separated and discarded. The remainingaqueous solution was dried in an oven to obtain a sodiumdodecylchlorodiphenyl oxide sulfonate product as a light yellow powderwhich was found to give a clear solution at concentration of 0.1% and 5%in 7% sodium hydroxide solution and was found to be insoluble in 17%sodium: hydroxide solution at either concentration. 'Ilhe 5% solution in7% sodium hydroxide had a surface tension of 30.3 dynes/cm. The powderhad a softening point of above 300 C.

EXAMPLE 6.SODIUM PENTADECYLCHLO- RODIPHENYL OXIDE DISULFONATE 22.2 grams(.054 mole) of pentadecylchlorodiphenyl oxide of Step (2) of Example 5was dissolved in 107 ml. of methylene chloride. To this solution therewas added 12.86 grams (.161 mole) of sulfur trioxide dissolved in 64 ml.of methylene chloride over a period of 11 minutes with stirring andcooling. It was stirred for an additional 56 minutes. The temperaturewas maintained at 10-20 C. during the reaction. The reaction mixture wasworked up as above to .give a light brownish powder which was soluble at5% concentration in 7% sodium hydroxide and insoluble in 17% sodiumhydroxide. The 5% solution had a surface tension of 32.2 dynes/c-m.

EXAMPLE 7 Employing dodecylbromodiphenyl oxide of Step (2), Example 5and the procedure of Step (3) of Example 5, there was obtained a sodiumdodecylbromodiphenyl oxide disulfonate having a softening point of270-280 C.

By a similar procedure but by use of only half as much sulfur trioxide,sodium dodecylbromodiphenyl oxide sulfonate was prepared. A 0.1 solutionof it in water had a surface tension of 32.2 dynes/cm. and aninterfacial tension against mineral oil of 1.8 dynes/cm.

It is readily apparent that in the synthesis of the compounds of theinvention one may, and usually does, obtain a mixture of cogenericproducts wherein the number of alkyl, halogen or sulfonate substituentson the diphenyl oxide nucleus has an average value other than the wholenumbers 1 or 2. Thus, a typical product may contain. an 7 soluble metalhydroxide or carbonate. Alternatively, one I may convert one salt toanother. Thus, to make the magnesium or iron salt, for instance, one mayadd an aqueous solution of a soluble iron or magnesiumsalt, such as thechloride or nitrate, to an aqueous solution of an alkali metal orammonium salt of the sulfonic acid. The magnesium and iron salts of thesulfonic acid, being substantially insoluble in water, are thusprecipitated.

The water soluble salts of the invention, i.'e., the alkali metal,ammonium and lower alkylamine salts, are highly effective surfactantsand are useful as the active ingredient of detergents, wetting anddispersing agents, emulsifiers, and the like. Specific applicationsinclude dish-washing and laundry detergents, toilet soap bars, shampoos,dry cleaning detergents, sanitizing detergents for scrubbing floors,dairy equipment, veterinary hospital rooms, pens and equipment, and thelike. They are also highly effective as dry cleaning detergents.

The dry cleaning industry employs a variety of waterinsoluble solventsfor cleaning soiled fabrics. These include perchloroethylene,trichloroethylene, carbon tetrachloride, Stoddard solvent, etc. It iscommon practice to add to these dry cleaning fluids varioussurface-active agents to remove water-soluble stains from the materialsture was necessary in order for the detergent to function properly andfor water-soluble soils such as salt, sugars and perspiration to beremoved. Any water-soluble salt or stain not removed during dry cleaningtreatment was later removed by a time-consuming and expensive methodknown as spotting. It was also found that the addition of too much waterwould cause shrinkage and wrinkling or have other detrimental effectsupon the fabric. Since that time the dry cleaning industry has had theproblem of finding means and solvent compositions which would maintainthe water concentration in the solvent within the limits required forefliciency of the detergent without adverse effects upon the fabric.

It has been discovered that if an alkali metal, amine or ammonium saltof an alkylated halogenated diaryl oxide sulfonic acid is added tosubstantially water-insolu ble dry cleaning fluid, a solvent compositionis produced which shows outstanding and unusual properties, both asconcerns cleaning effectiveness and as concerns control of effectivewater concentration in the solvent. The dihalomonosulfonates areespecially suitable for this purpose. In the commercial dry cleaningpractice it was found that the relative vapor pressure of water (P/Powhere P and P0 are, respectively, the partial pressure of water vapor inequilibrium with the composition and with pure water) in the drycleaning solvent containing a soap or detergent was an important factorin determining the acceptability of the solvent and this value becameknown as solvent relative humidity. A study of this problem is to befound in ASTM Bulletin for September of 1953 on pages 65-68 (TP 153 etseq.). It was established that if the solvent relative humidity was lessthan 0:65

the soap or detergent would not function properly in the removal ofwater-soluble soils and stains in the material. f

of the system increases because of the water carried by the fabric.

The rate of increase of solvent relative humidity with increasing watercontent is dependent upon the particular soap or detergent employed withthe solvent and upon its concentration. It is obviously desirable that asolventdetergent composition be employed wherein the rate of increase ofsolvent relative humidity with increasing water concentration be as lowas possible. The solvent relative humidity for a system containing anygiven amount of soap or detergent, however, cannot be predicted inadvance by any method currently known.

It is surprising, therefore, to find that the use of an alkylatedhalogenated diphenyl oxide sulfonate salt with any of the known drycleaning solvents produces a solvent-detergent mixture with an abilityto allow the addition of greatly increased quantities of water and stillre main within the desired solvent relative humidity range. In additionto this advantage, a combination of dry cleaning solvent with ahaloalkyldiphenyl oxide sulfonate salt shows an improved ability toremove water-soluble soils. To the dry cleaning industry this means areduction of spotting and a greatly simplified dry cleaning procedure.The dry cleaning solvent, in order to obtain a dry cleaning compositionhaving the highly desirable characteristics, should contain about 0.25to 20%, and preferably about 3 to 6%, by weight, of the alkylatedhalogenated diphenyl oxide sulfonate salt.

In order to obtain solvent relative humidity values for the compositionsof this invention and to have a standard method for comparison of thesevalues with those obtainable with known solvent-detergent systems,standard ASTM equipment and procedures were employed. The steps of'thisprocedure and equipment employed are described in more detail in ASTMBulletin (PB 153) for September, 1953 on pages 6467. The procedurefoltaining 20 grams of the detergent to be tested into a 1000 cc.-flask. The flask was placed in a constant-temperature oven at 80 F. andstirred with a hollow impeller connected to a hollow shaft. As theimpeller was rotated, air was forced through the solvent, past ahumiditysensing element which was connected to a recorder and backthrough the hollow shaft and impeller into the solvent. The stirring wascontinued until the recorder indicated that equilibrium had beenreached. At this time about 0.5 gram of water was added to the systemand stirring was continued until equilibrium was again reached. Thisprocess was continued until a solvent relative humidity of about 90 hadbeen obtained. The results of several such experiments are shown in thetable below, wherein the relative humidity of the solvents at variouswater contents is shown. From these data it is evident that thedetergents of the present invention tolerate a much higher water contentin the dry cleaning fluid without exceeding the desirable humidity rangethan do the detergents currently used in the industry.

lowed was to place 500 cc. of dry cleaning solvent con- 8 ers areconfronted with two widely dissimilar types of soil to be removed fromfabrics: (1) water-soluble soils, typified by perspiration stains and(2) water-insoluble soils typified by dirt, greases, and the like. Sincemany detergents which are highly effective in removal of one type areineffective with the other and since it is highly desirable that adetergent be effective with both, tests were set up to measure theeffectiveness of our compounds with both types of soil. These tests andthe results thereof .were as follows:

Water soluble removal test (1) A 4-inch wide strip of rayon white crepe,approximately 30 yards long, is passed through a 1.5 N NaCl solution, aclothes wringer, over a bank of drying lamps, and then wound onto atake-up reel.

(2) Swatches are cut from the roll at 4-inch intervals and numberedconsecutively.

(3) Every 20th swatch is set aside for a salt content determination.These are the blanks.

(4) Determination of the salt content of swatches is as follows: A blankswatch is weighed, placed in a 250 ml. Erlenmeyer flask and 75 to 100ml. of deionized water is added. Fluorescein indicator is added and thecontents titrated with .1 N AgN0 The presence of the swatch does notinterfere with the end point. The salt content of the swatches iscalculated from this data.

(5) The remaining swatches are individually weighed and their weightsrecorded.

(6) Various percentages of detergent are dissolved into sufiicientsolvent to make 1600 ml. of solution. Suflicient water is then added toproduce a 75% solvent-relative humidity.

(7) Four hundred ml. of the above solution is put into eachTerg-O-Tometer beaker.

(8) Two swatches are placed in the solution in each beaker and theTerg-O-Tometer operated for 30 minutes at 75 cycles per minute and 75 F.

(9) The Terg-O-Tometer is stopped, the swatches are removed, drained,and permitted to dry by suspending them from a line in a hood.

10) Each air dried swatch is placed in a 250 ml. Erlenmeyer flask andits salt content determined as in Step (4). Y

(11) The percent salt removal is calculated from the data.

Carbon soil removal TABLE I.-WATE R TOLERANCE OF DRY CLEANINGCOMPOSITIONS Relati o humidit ereent as a funeti f e 'igast SolventDetergent v y (p on o Wat r content 1 C101 Petroleum sulfonate l 66 7584 2 C 01 Fatty amine condensate I 57 66 72 80 82 3 C 014.P%1tagecyldichl0rodiphenyl oxide 58 71 79 88 3 8. 4 C 014-rtgiergyl-4'ehiorodiphenyl oxide 32 48 58 73 75 79 88 a a. 5 VarsolPtgiagecyldichlorodiphenyl oxide 44 51 55 59 63 66 70 74 79 1 Commercialdetergents widely used in the dry cleaning industry. 3 Commercialsolvent widely used in the dry cleaning industry.

Representative compounds of the invention were further evaluated as drycleaning detergents by determining their detergent properties in thisapplication. Dry clean- (5) Remove swatches, drain and suspend on a linein a hood until dry.

(6) The search unit of a Model 610, Photovolt Re- .9 flectometer isplaced over an unsoiled swatch supplied by vendor and the. galvanometerneedle set on 100.

. (7) The search unit is placed on an unwashed soiled swatch and thegalvanometer needle adjusted to zero.

(8) Measure the reflectance of the washed swatch. The galvanometer nowreads directly in percent .soil removal. Y

- Whireness retention (1) Disperse a given weight of either carbon blackor fine floor sweepings in the solution.

(2) The percent detergent used was varied from 1.25 to 2.5%. v

V (3) Four hundred mls. of solution was added to each of theTer'g-O-Tometer beakers.

(4) Place two 15-inch by 6-inch swatches of unsoiled white rayon in eachbeaker.

(5) Agitate for minutes.

(6) Remove swatches, drain, and suspend from a line in a hood until dry.

(7) Measure the reflectance of the soiled fabric.

(8) Make similar tests with no detergent added;

(9) Calculate whiteness retention using the formula Reflectance aftersoiling X Pereent whiteness Reflectance unwashed fabric retention In thefollowing tests, perchloroethylene, the most widely used dry cleaningsolvent, was used. The concentration of the detergent in this solvent isexpressed as percent by weight. Similar results are obtained when othercommercial dry cleaning solvents are used instead of perchloroethylene.

TABLE II Percent Cone. of removal detergent,

percent whiteness retention, percent Detergent Sol.

Insol. soil soil Bis-(2-hydroxyethyl)- ammonium dodocylchlorodiphenyloxide sulfonate.

2-hydrpxyethylam- 2. 50

monium dodecylchlorodiphenyl o ide sulfonate.

' Triethylanunonlum dodocylchlorodiphenyl oxide suitonate.Bis-(2-hydroxyethyl) ammonium dodecyldichlorodiphenyl oxide suli'mate.Sodium dodeoylchlorodlphenyl oxide sullonate.

I Not measured.

- Many of the new compounds, especially the monohalo disulfonates areuseful in surface active compositions used in cellulose chemical pulpproduction as described .in Canadian Patent No. 381,129 because they aresoluble in 5 to 8% caustic and insoluble in 17 to 22% caustic(mercerizingor steeping strength). The compounds useful for this'purposeincludethose having the formula mor solvent-detergent-water the activealkylhalodiphenyl oxide sulfonate, a marked" residual bacteriostatic andfungistatic effect is observed; i.e., not only is the growth of themicrobes then on the washed object substantially inhibited but theinhibitory efiect persists for days thereafter. While these effects arestrongest when alkylhalodiphenyl oxide sulfonates are used as the soledetergent, it is also observed when they constitute only a smallpercentage of the active detergent, the major portion thereof being anyconventional detergent having no unusual anti-microbial property.

' In the formulation of commercial detergent products such as laundry ordish-washing detergent powders orfi builders, extenders,anti-redeposition agents, brighteners, foam modifiers, and the like,each of which then performs itsnor-mal function. Thus, useful builtdetergent compositions are obtained by combining a builder with acompound having the formula wherein R is an alkyl radical containing 12to 22 carbon atoms, X is a halogen having an atomic number from 17 to35, m and n are integers from 1 to 2 and M is' a water-solubilizingmonovalent cation, preferably analkali metal or hydroxyalkylammoniumradical.

applications.

EXAMPLE 8 A laundering bath comprising 1 gram per liter of sodiumtripolyphosphate, 0.01 gram per liter of carboxymethyl cellulose and 0.4gram per liter of sodium dodecylchlorodiphenyl oxide sulfonate preparedas described in Example 3 was employed to wash samples of artificiallysoiled fabric in a U.S. Testing Company Terg-,

O-Tometer and the washed cloths compared for whiteness measured inreflectance units on a reflectometer. A

control of unwashed fabric was also measured.- The results of such testsare recorded in the table below:

TABLE III Reflectance of artificially soiled cotton cloth Surfactant ACHl ACH Dodecylmonochlorodlphenyl oxide monosodium sullonate 49. 5 44. 8Alkylbenzene sulfonate 48. 7 44. 6 Unwashed 22.0 27.0

1 Types of artificially soiled cotton cloth manufactured by AmericanConditioning House.

EXAMPLE 9 5 m1. of-a 24-hour culture of Micrococcus pyogenes var. aureus(Strain ATCC 209), also known as "Staphy-,- lococcus aureus, in peptonebroth was mixed with 50 ml. of a molten nutrient agar at 50 C. 5 m1. ofthis mix: Y

d'iphenyl oxide sulfona-te as well as an area around the detergent g Thefollowing examples are typical illustrations of the above Fabrics washed1 1 perimeter of the cloth of /2 millimeter width was found to besubstantially free from the growth of the bacterial organism. The areasunder the cloth washed with dodecylbenzene sulfonate or sodium laurylsulfate showed the growth of numerous colonies of the bacterialorganism.

In tests similar to that above, fabrics that-had been I dry cleaned asdescribed above under the Soil Removal Tests were tested for residualantimicrobial activity.

' Results are summarized in Table IV.

It has been noted that the residual bacteriostatic and fungistaticproperties of articles washed or otherwise contacted with thecompoundsof the invention is considerably enhanced if polyvalent metal ions arepresent. This is thought to be due to the precipitation on the treatedarticle of the insoluble or difficulty soluble poly-' valent metal saltof the alkylhalodiphenyl oxide sulfonic acid. Ordinary domestic watersupplies contain sufiicient hardnes to produce this effect althoughadditional soluble salts, such as calcium or magnesium chloride,sulfate, carbonate or the like may be added to the treating solution ifdesired. Among the salts that have been found especially effective forthis purpose are those of calcium, zinc, magnesium, copper, mercury andiron.

Other suitable salts include those of aluminum, manganese, barium, lead,silver, cadmium, and, in general, any metal having a valence of up tothree. Such salts of any of the alkylh-alodiphenyl oxide sulfonic acidsof the invention areapparently effective for the purpose.

In a series of antimicrobial tests of various compounds of thisinvention the compound to be tested was dissolved in sterile distilledwater and portions of this solution were mixed into A. O.A.C. broth toproduce concentrations therein of 0, 2.5, 5, 7.5, 10, 25 and 50 partsper million, by weight. Tubes of these broths were then inoculated witha 24-hour culture of Staphylococcus aureus and incubated at 37 C. for 48hours. They were then read for growth or no growth. Some typical resultsof such tests are shown in Table V.

In 'I'a-ble V two numbers are shown under the heading InhibitoryConcentration. The first is the highest tested concentration at whichgrowth of the bacteria was observed while the second is the lowesttested concentration which prevented growth.

TABLE V.INHIBITION or onow'rrr F STAPHYLO- g cocc'us AUREUS Inhibitoryconcen- TABLE V---6'onttn-uad Inhibitory concen- Compound: tration,p.p.m.

Na pentadecylchlorodiphenyl oxide sulfonate 25-50 Napentadecylbromodiphenyl oxidesulfonate 25-50 Na dodecyliododiphenyloxide sulfonate 25-50 Na docosanylchlorod'ip'henyl oxide disulfonate50-100 In other tests similar to those reported in Table V, the abilityof the compounds of the invention to inhibit the growth of othermicroorganisms was measured. The procedure was the same as thatdescribed above except that in the case of Corynebacterium diphtheriaethe culture medium was a brain-heart infusion broth and the cultures ofBacillus subtilis and Bacillus cereus were incubated IO'days beforebeing read.

Results of these tests are shown in the following table.

Sodium dodecylchlorodiphenyl oxide sulfonate was the growth inhibitor ineach of these experiments.

TABLE VI.INHIBITION OF GROWTH OB VARIOUS MICROORGANISMS Inhibitoryconcen- Organism: tration, p.p.m.

Bacillus subtilis 10-25 Bacillus cereus 10-25 Corynebacteriumdiphtheriae 5-10 M icrococcus pyogenes var. aureus #209 2.5-5Micrococcus pyogenes var. aureus /81 5-10 Micrococcus pyogenes var.albus 5-10 Micrococcus pyogenes var. aureus Queens Geneal' Hospital a5-10 Streptococcus viridans 10-25 Hemolytic Streptococcus 5-10 It hasbeen found that the alkali metal salts and other pharmaceuticallyacceptable salts of the sulfonic acids of the invention aresubstantially non-irritating to animal tissues and non-toxic whenusedinternally or externally, or even when injected, in antimicrobialconcentrations.

This makes them highly desirable as active components of householddetergents, toilet soaps and detergent bars, shampoos, cosmetic creams,lotions, powders and the like, foot powders, body dusting powders,ointments, salves, pharmaceutical creams and injectable antibiotics.Some of these applications are illustrated by the following examples.

EXAMPLE 10 A typical laundry detergent having antimicrobial properties:

Parts Sodium dodecylchlorodiphenyl oxide sulfonate 20 Sodiumtripolyphosphate :50 Sodium carboxymethyl cellulose 0.5

EXAMPLE 11 2400 grams (20.2% by weight) of sodium dodecylchlorodiphenyloxide sulfonate, 5065 grams (61.7%)0f the coconut acid ester of sodiumisethionate (Igepon AC 78, a commercial product), 640 grams (7.7%) ofzinc stearate and 80 grams (.9%) of titanium dioxide were mixed togetherand passed twice through a 3-roll mill to obtain a smooth ribbon. Theribbon was then passed through a soap plodder several times to insureuniform mixing and then plodded into a long rod which was then cut andpressed into bars about 1 inch thick and 3 inches square. The bar wasthen employed in the treatment of fungus diseases such as athlete's foot(Tinea pedis) by washing the affected area with the bar twice daily fora period of 3 weeks. At the end of this period, marked relief of thefungus growth was observed as evidenced by healing of the scale and rawarea of the affected portions. A control was run employing a compositionsubstantially identical with the above except that no diphenyl oxidederivative was present. Washing the affected area with the control for aperiod of 3 weeks resulted'in no improvement or relief.

EXAMPLE 12 750 grams (22.8%) of sodium dodecylchlorodiphenyl oxidesulfonate, 2250 grams (68.2%) of Ivory Soap Flakes, and 300 grams (9.0%)of water were milled, ploded and pressed into bars in the manner ofExample 11. This soap was excellent as a hand or bath soap, having adesirable hardness, feel and rate of dissolving. It produced abundantlather having excellent cleaning.

The bars were employed to treat athletes foot by washing the atfectedarea. Within 3 weeks relief of rawness and itching was evidenced.Controls wherein the affected areas weresimilarly washed with a bar ofIvory soap showed no relief.

The compounds of the invention, when used in soaps, ointments, dustingpowders or lotions, have shown a beneficial soothing eifect andreduction or elimination of itching or irritation in various other skindisorders, such as diaper rash and dandruff and on flea bites and fungusinfections on dogs.

The symbol M is used herein to represent a cation. It is to beunderstood that wherever M is used, the cation is present in sufiicientquantity to satisfy the valence of the sulfonate radical with which itis associated. Thus, in the radical -SO M, it is to be understood that Mrepresents '1 molar proportion of a mono-valent cation, /fi molarproportion of a divalent cation or )6 molar proportion of a trivalentcation. We claim:

.1. A germicidal detergent composition comprising a detergent builder inan amount effective to improve the detergent properties of thecomposition and a compound corresponding to the formula 6 wherein R isan alkyl radical containing 12 to 22 carbon atoms; X is a halogen havingan atomic number form 17 to 35; m and n are integers from 1 to 2 and, Mrepresents a water-solubilizing monovalcnt cation.

2. A germicidal detergent composition as defined in claim 1 wherein M isan alkali metal.

3. A germicidal detergent composition as defined in claim 1 wherein M isa hydroxyalkylammonium radical.

4. A germicidal detergentcomposition as defined in claim 1 wherein thedetergent builder is sodium tripolyphosphate.

5. A germicidal detergent composition consisting essentialy of (A) asthe active detergent, one part by weight of sodiumdodecylrnonochlorodihpenyl oxide monosulfonate and (B) as a builder,about 2.5 parts of sodium tripolyphosphate.

6. A-composition consisting of an aqueous solution of about 5 to 8%, byweight, of sodium hydroxide and 0.1 to 5% of a compound having theformula i so wherein R is an alkyl radical containing 12 to 15 carbonatoms, X is a halogen having an atomic number of 17 to 35 and M is 'analkali metal.

JULIUS GREENWALD, Primary Examiner.

A. T. MEYERS, Assistant Examiner.

1. A GERMICIDAL DETERGENT COMPOSITION COMPRISING A DETERGENT BUILDER INAN AMOUNT EFFECTIVE TO IMPROVE THE DETERGENT PROPERTIES OF THECOMPOSITION SAID A COMPOUND CORRESPONDING TO THE FORMULA